JPH0886769A - Electrode body - Google Patents

Abstract

PURPOSE: To secure electrical conductivity inside an electrode main body for smooth measurements by easily removing bubbles existing inside a tube or the like for smooth circulation of an internal liquid and stabilization of outflow pressure. CONSTITUTION: This electrode body consists of an electrode main body 1 with a tube 7 connected to its internal liquid replenishing hole 6a so that an internal liquid for a reference electrode is supplied via the tube 7 into an internal liquid chamber 2 inside the electrode main body 1 from the outside. Time main body has a through hole 10 therein which communicates with the internal liquid chamber 2 and a plug 13 which can be handled to close the through hole 10 during measurement and to vent the internal liquid chamber 2 to atmosphere via the through hole 10 during removal of bubbles existing in the tube 7, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a composite electrode for measuring pH, ORP (oxidation-reduction potential) or the like, or a unipotential type reference electrode, which is connected to an internal liquid chamber for the reference electrode via an external tube. The present invention relates to an electrode body of the type that supplies a liquid.

[0002]

2. Description of the Related Art FIG. 6 is a sectional view showing an example of a conventional industrial pH composite electrode. In the figure, 101 is a cylindrical electrode holder, 102 is a holder cap attached to the upper end of the electrode holder 101, and 103 is the electrode holder 101.
A protective cylinder attached to the lower end of the electrode 104, an electrode body 104 including a glass electrode 105, a reference electrode and a liquid junction 106 thereof, 107 a gasket holding the electrode body 104,
Reference numeral 108 is a lead wire that connects the electrode body 104 and an external measurement circuit.

This pH composite electrode is used by immersing the electrode body 104 in a test liquid in various processes, and the electrode holder 101 supplies KCl to the reference electrode.
Also serves as a tank for replenishing internal liquids such as. 10
Reference numeral 9 is an internal liquid, 110 is an internal liquid replenishing port formed in the electrode body 104, and 111 is an internal liquid replenishing port formed in the electrode holder 101 and the holder cap 102.

The above-mentioned pH composite electrode is an electrode holder 101.
Has the advantage that it also serves as a tank for replenishing the internal liquid, but since the electrode holder 101 may reach a maximum length of about 3 m, the entire electrode body becomes heavy, which makes it inconvenient to carry and supports the electrode body. The structure also requires considerable strength. There is also a problem that a stable outflow pressure cannot be obtained because the outflow pressure of the internal liquid 109 from the liquid junction 106 depends on the remaining amount.

In view of these points, recently, there has been provided an electrode body of a type in which an internal liquid is supplied to a reference electrode from a tank provided outside via a tube. With this electrode body, it is possible to reduce the weight of the electrode holder due to the downsizing, and it is also possible to stabilize the outflow pressure of the internal liquid.

The electrode body capable of supplying the internal liquid by the above-mentioned tube is a glass electrode 105 as shown in FIG.
Unlike the one in which the liquid junction portion 106 and the liquid junction portion 106 are fixed to the electrode main body 104, a glass electrode and a liquid junction portion, which are consumable items, are formed in a chip shape and are a chip exchange type electrode body in which these can be replaced, Various items have been provided (Japanese Patent Laid-Open No. 58-58).
-See 61457).

[0007]

In the case of the tip exchange type electrode described above, in which an electrode body for supplying the internal liquid by a tube is newly provided, the electrode body and the tube are connected in the field. At that time, if air bubbles enter the tube or reference electrode, the internal liquid will not be smoothly supplied from the tank, the internal liquid outflow pressure will become unstable, and the conductivity between the internal battery and the liquid junction will decrease. Therefore, it is necessary to remove the air bubbles by some method because there is an inconvenience that the measurement is hindered. This problem can occur not only when the electrode body is connected to the tube but also when air bubbles are generated due to a phenomenon such as dissolved air becoming small bubbles during normal measurement thereafter.

This type of electrode body has an airtight structure except for the internal liquid replenishment port and the liquid junction, and it is expected that air bubbles will naturally escape toward the tank through a thin tube having an inner diameter of about 4 mm. Therefore, conventionally, the liquid junction is once pulled out from the electrode body, and the electrode body is turned upside down to let air bubbles in the tube or the like escape to the atmosphere. However, it may not be possible to invert the electrode body depending on the installation environment of the electrode body, so the method described above is not the best method.

The present invention has been made in order to solve the above problems, and its purpose is to easily remove bubbles existing in a tube or the like to allow the internal liquid to smoothly flow and to cause no trouble. It is to provide an electrode body that can perform measurement.

[0010]

In order to achieve the above object, the first invention according to claim 1 is that a tube is connected to an internal liquid replenishing port of the electrode body, and the inside of the electrode body is connected through the tube from the outside. In the electrode body for supplying the internal liquid to the internal liquid chamber for the reference electrode, the through hole communicating with the internal liquid chamber and the through hole during the normal measurement are sealed to remove air bubbles existing inside the tube or the like. And a stopper operable to open the internal liquid chamber to the atmosphere through the through hole.

According to a second aspect of the present invention, a tube is connected to the internal liquid replenishing port of the internal liquid tank mounted on the electrode body, and the internal liquid supplied from the outside to the internal liquid tank via the tube is supplied. In the electrode body that supplies the internal liquid chamber for the reference electrode in the electrode body, the through hole that communicates with the inside and outside of the internal liquid tank and the through hole is closed at the time of measurement, and the through hole is used when removing bubbles. And a stopper operable to open the internal liquid tank to the atmosphere.

[0012]

In the first aspect of the invention, the internal liquid chamber is opened to the atmosphere through the through hole by the operation of the stopper, and the second liquid chamber is provided.
In the invention, the internal liquid tank is opened to the atmosphere through the through hole by operating the stopper. By pumping the internal liquid from the tube in this state, bubbles existing in the tube, the internal liquid chamber, the internal liquid tank, or the like are pushed out and discharged to the outside through the through hole.

[0013]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a perspective view showing a first embodiment of the first invention described in claim 1, and is a case where the present invention is applied to a chip exchange type pH composite electrode. In the figure, reference numeral 1 denotes an electrode main body, and a glass electrode, a reference electrode, a temperature compensating electrode, etc. are provided inside thereof. Where the glass electrode,
For the sake of convenience, the temperature compensation electrode is not shown.
An internal liquid chamber 2 forming a reference electrode is formed inside the electrode body 1, and a liquid junction 3 made of ceramic or the like is detachably attached to the lower end of the internal liquid chamber 2.

The internal liquid chamber 2 communicates with an internal liquid supply chamber 5 through a slit 4, and this internal liquid supply chamber 5 is
An internal liquid replenishing port 6a provided in the cap 6 communicates with a transparent tube 7. The other end of the tube 7 is K
It is connected to an internal liquid tank (not shown) such as Cl. Reference numeral 8 is a lead wire connecting each electrode and an external measurement circuit.

In the cylindrical casing 9 of the electrode body 1,
A circular through hole 10 for removing bubbles is formed in a portion located at the upper end of the internal liquid chamber 2. The through hole 10 communicates with the internal liquid chamber 2 through a small-diameter passage 11, and an O ring 12 is housed in the bottom of the through hole 10. Here, exemplifying the inner diameters of the through hole 10 and the passage 11 are 6 mm and 2 mm, respectively.

Reference numeral 13 denotes a minus-screw-like plug body screwed into the through hole 10. When the plug body 13 is screwed in, the inside and outside of the casing 9 are kept liquid-tight by the action of the O-ring 12. Therefore, the measurement can be performed without leaking the internal liquid. The plug 13 and the O-ring 12 have the same heat resistance as the main part of the electrode body 1.
It is made of a material having chemical resistance and pressure resistance, and this is the same in each of the following examples.

Next, the bubble removing structure including the plug 13 will be described in detail with reference to FIG. 2A is a cross-sectional view of the through hole 10 with the plug 13 being screwed in, and FIG. 2B is the plug 13.
FIG. This plug body 13 is formed by threading the outer peripheral surface of a cylinder, forming a minus groove 13a on one end surface in the axial direction, and forming a pair of parallel ventilation grooves 13b on the outer peripheral surface so as to be orthogonal to the minus groove 13a. It will be. In addition, the ventilation groove 13b is formed along the axial direction of the plug body 13 by 3
More than one book may be formed. Further, a plus groove may be provided instead of the minus groove 13a.

The air bubble removing operation in this embodiment will be described below. For example, when air bubbles are present in the tube 7,
The stopper 13 is slightly loosened by using a jig such as a flat-blade screwdriver, and the stopper 13 is moved so that its one end surface is separated from the O-ring 12, as shown by a dashed line in FIG.
As a result, the internal liquid chamber 2 has the passage 11 and the through hole 10.
It communicates with the outside of the casing 9 through the O-ring 12 side space and the ventilation groove 13b, and is opened to the atmosphere.

Therefore, when the internal liquid is pressure-fed from the tank side, the bubbles in the tube 7 reach the upper end of the internal liquid chamber 2 through the internal liquid supply chamber 5, and further, the ventilation groove 13 is formed in the above-mentioned path.
It will be discharged into the atmosphere from b. At this time, some internal liquid may leak to the outside together with the bubbles. However, if the plug 13 is quickly screwed in after removing the bubbles, a small amount of the internal liquid will leak, which is a practical problem. It doesn't.

Further, even when air bubbles remain near the upper end of the internal liquid chamber 2, if the stopper 13 is loosened in advance and the internal liquid is pressure-fed from the tube 7, the internal liquid causes the air bubbles to pass through the passage 11. In the same direction, and vent groove 13b as above
To be released into the atmosphere. Although not shown, even when the through hole 10 and the internal liquid supply chamber 5 are connected by the passage 11 so that the through hole 10 and the internal liquid chamber 2 are indirectly communicated with each other, substantially the same action and effect as described above are obtained. It is possible. According to this embodiment, the structure of the plug body 13 and the through hole 10 is relatively simple, and the members can be easily processed at low cost.

Next, FIG. 3 shows a second embodiment of the first invention, and like FIG. 2, (A) is a sectional view of the through hole 10A with the plug 13A screwed in, The same (B) is a plug 13A
FIG. 13 A of plug bodies are formed in the convex shape in a cross section by continuously arranging the cylinders with different diameters in the axial direction, and the outer peripheral surface of the cylinder with the larger diameter is threaded. Inside the plug body 13A, an L-shaped vent hole 13c is formed that connects the through hole 10A and the minus groove 13a. On the other hand, through hole 1
0A is 2 in the axial direction so as to match the shape of the plug 13A.
The O-ring 12 is formed in a step and is arranged in a step portion on the side of the passage 11.

As the operation of removing bubbles, the stopper 13A is loosened and moved as shown by the one-dot chain line in FIG. 3 (A), whereby the internal liquid chamber 2 is provided with the passage 11 and the space on the O-ring 12 side of the through hole 10A. And communicates with the outside of the casing 9 through the vent hole 13c and is open to the atmosphere. Therefore, if the internal liquid is pressure-fed from the tank side, the bubbles in the tube 7 and the internal liquid chamber 2 will escape to the atmosphere from the vent hole 13c through the above-mentioned path. When the plug 13A is screwed in, the passage 11 is closed by the O-ring 12 and is in a liquid-tight state, so that the internal liquid does not leak out of the casing 9 during measurement.

In this embodiment, if one vent hole 13c is provided, it is possible to remove air bubbles as desired.
If a portion that coincides with the central axis of the plug 13A (the long portion of the vent hole 13c) is common and a plurality of opening portions (portions orthogonal to the above long portion) to the through hole 10A are radially formed, air bubbles It can be discharged more quickly.

FIG. 4 is a sectional view of a through hole 10B and a plug 13B showing a third embodiment of the first invention. In the plug body 13B of this embodiment, a conical needle portion 13d is formed on one end face in the axial direction of a cylinder whose outer peripheral surface is threaded, and the needle portion 13d is inserted into the passage 11 when the plug body 13B is screwed. It is configured to seal a part of the inner peripheral surface.

As in the first embodiment, the plug 13B is formed with a minus groove 13a and a ventilation groove 13b. When the plug 13B is loosened, the ventilation groove 13b is passed from the passage 11 through the through hole 10B. Bubbles are discharged along the route to. Although not shown, the ventilation hole 13c may be provided instead of the ventilation groove 13b as in the second embodiment. In this example, the first,
The O-ring 12 in the second embodiment is unnecessary, the number of parts is reduced, and the labor for replacement, inspection, etc. accompanying it is reduced.

Although each of the above-mentioned embodiments relates to a tip exchange type electrode body, the first invention does not require the tip of the liquid junction to be pulled out at the time of removing air bubbles, so that the usual fixed type ( It is also applicable to (non-exchangeable) electrode body. Therefore,
The present invention enables the supply of the internal liquid to the fixed electrode body by the tube, which has been impossible in the past.

Next, FIG. 5 shows an embodiment of the second invention described in claim 2. The present invention is directed to an electrode body of a type in which an internal liquid tank connected to a tube for replenishing the internal liquid can be attached to and detached from an electrode body as an attachment. It can be applied to both types of electrode bodies regardless of formula.

That is, in FIG. 5, the electrode body 104 is the same as that shown in FIG. 6, and the glass electrode 105 and the liquid junction portion 106 of the reference electrode are fixed. Further, although the internal liquid replenishing port 110 provided in the electrode body 104 communicates with the internal liquid chamber in the comparison electrode, these connection configurations are omitted in the figure. 15 is an internal liquid replenishment port 15a
A pair of O-rings 17 and 1 that are substantially hollow cylindrical internal liquid tanks connected to the
It is mounted in a liquid-tight state on the electrode body 104 via 8.

A through hole 16 and a passage 19 are provided in the upper portion of the side surface of the internal liquid tank 15 as in the first embodiment of the first invention, and the inside of the through hole 16 is provided with an O ring 20 as shown in FIG. The stopper 13 is screwed in. That is, in this embodiment, the bubble removing structure including the through hole 10, the passage 11 and the plug 13 provided in the casing 9 of the electrode body 1 in FIG. 2A is applied to the side wall of the internal liquid tank 15. It is a thing.

Also in this embodiment, the bubbles existing inside the tube 7, the internal liquid tank 15, the internal liquid chamber of the reference electrode, etc. can be promptly discharged to the outside by operating the plug 13. It is also possible to apply the second or third embodiment of the first invention shown in FIG. 3 or 4 to the bubble removing structure provided on the side wall of the internal liquid tank 15.

According to this embodiment, the internal liquid can be constantly supplied to the electrode body 104 by the tube 7 and the internal liquid tank 15 without using the elongated electrode holder 101 as shown in FIG. The bubbles existing inside the internal liquid tank 15 and the like can be reliably removed.

Each of the above-mentioned embodiments is one in which the first or second invention is applied to a pH composite electrode. However, each invention is an ORP composite electrode and various ions in which a measurement electrode and a reference electrode are integrated. It can be applied to a selective composite electrode and a unipotential reference electrode.

[0033]

As described above, according to the first or second aspect of the present invention, the electrode body is opened to open the through hole and open the internal liquid chamber or the internal liquid tank to the atmosphere by operating the stopper. There is an effect that bubbles can be easily removed without resorting to complicated means such as inversion. This makes it possible to smoothly flow the internal liquid, stabilize the outflow pressure from the liquid junction, and ensure the conductivity of the electrode body.

Further, since it can be applied to both tip exchange type and fixed type electrode bodies, it has high versatility, and it is not necessary to store a large amount of internal liquid in the electrode holder, so that the weight can be reduced. it can. Further, the structure is relatively simple, and it can be realized by slightly modifying the conventional electrode body or adding parts, so that it is excellent in economic efficiency.

[Brief description of drawings]

FIG. 1 is a perspective view showing a first embodiment of the first invention.

FIG. 2 is an explanatory view of a bubble removing structure in the first embodiment of the first invention.

FIG. 3 is an explanatory diagram of a bubble removing structure in a second embodiment of the first invention.

FIG. 4 is an explanatory view of a bubble removing structure in a third embodiment of the first invention.

FIG. 5 is a sectional view of a main portion showing an embodiment of the second invention.

FIG. 6 is a diagram showing an example of a conventional industrial pH composite electrode.

[Explanation of symbols]

 1,104 Electrode Main Body 2 Internal Liquid Chamber 3,106 Liquid Junction 4 Slit 5 Internal Liquid Supply Chamber 6 Caps 6a, 15a, 110 Internal Liquid Replenishment Port 7 Tube 8 Lead Wire 9 Casing 10, 10A, 10B, 16 Through Hole 11 , 19 Passages 12, 17, 18, 20 O-rings 13, 13A, 13B Plugs 13a Minus groove 13b Vent groove 13c Vent hole 13d Needle part 15 Internal liquid tank 105 Glass electrode

Claims (2)

[Claims] 1. An electrode body, wherein a tube is connected to an internal liquid replenishing port of an electrode main body, and the internal liquid is supplied from the outside to the internal liquid chamber for a reference electrode in the electrode main body through the tube, It is characterized by comprising a communicating hole and a stopper operable to seal the communicating hole during measurement and to open the internal liquid chamber to the atmosphere through the communicating hole when removing air bubbles. The electrode body to do. 2. A tube is connected to an internal liquid replenishing port of an internal liquid tank mounted on the electrode body, and the internal liquid supplied from the outside to the internal liquid tank via the tube is supplied to the internal electrode for comparison electrodes in the electrode body. In the electrode body supplied to the liquid chamber, a through hole communicating with the inside and outside of the internal liquid tank and the through hole is closed at the time of measurement, and when removing bubbles, the internal liquid tank is exposed to the atmosphere through the through hole. An electrode body comprising a stopper operable to open.